Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D35/00—Producing footwear
  • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D35/00—Producing footwear
  • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
  • B29D35/14—Multilayered parts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
  • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2410/00—Soles

Definitions

• Polymers are obtained from the polymerizing units in the form of beads, etc.
• the polymerizing units are combined with equipment, in which the formed polymerized materials are processed after the introduction of the corresponding additives and fillers in order to obtain articles shaped by spinning, extrusion, molding etc.
• the finished products require prior formulation of the polymerized material, it is common practice to introduce fillers, additives and reinforcing material that can be selected in terms of the combinations of polymer and the desired effects.
• the later inclusion of the reinforcing material requires careful and controlled homogenization of the mixture (polymerized material+reinforcing material) in mixing operations with an energy requirement that is a function of the viscosity of the mixture (which also depends on the temperature, the molecular weight of the polymer and on the polymer/reinforcing material weight ratio).
• an energy requirement that is a function of the viscosity of the mixture (which also depends on the temperature, the molecular weight of the polymer and on the polymer/reinforcing material weight ratio).
• thermoplastic polymers reinforced by conventional means The technology concerning the production of thermoplastic polymers reinforced by conventional means is adequately described in Patent No. 677,296 awarded to Giulini Chemic GmbH on Mar. 4, 1985, included herein by reference.
• This patent deals with the reinforcing of polymer materials (especially epsilon caprolactone polymers, elastomer polyurethanes, modified polyolefins, etc.).
• thermoplastic materials are used in the footwear industry to form and retain the structure of the toe and heel of the shoe, in fusion with reinforcing fillers in particles 50 to 500 microns in diameter.
• reinforced thermoplastic sheets are obtained, from which pieces are then cut to reinforce the toe and heel of footwear in general.
• the material can be shaped, copying the last, and acting like a plastic material above a specified temperature that is called the activation temperature, then becoming elastic again and retaining the memory of the last once it cools.
• the activation temperature a specified temperature that is called the activation temperature
• the material it is desirable for the material to be able to adhere to the reinforcing materials; in some cases, one side is sufficient, but in other cases it is appropriate that it be able to adhere to both the lining and cap side.
• the most appropriate feature in the manufacture of footwear is for the material to have heat-sensitive adhesive qualities so that, when heated above the activation temperature, the adhesive melts and penetrates the other material superficially and continues to adhere after it has cooled down. These are the characteristics of thermoadhesion.
• the adhesive in some cases, it is appropriate for the adhesive, as it melts, to liquefy more on one face than on the other. This is the case, for example when a dressed leather is to be glued to one face and a very fine fabric to the other.
• the toecap material does not need adhesive on both sides, because no linings are put in since they are not visible.
• materials can be used that include the lining material in the reinforcement, laminated on the face that is visible so as to eliminate the lining in the construction of the shoe.
• thermoplastic polymer usually carboxylated butadiene styrene.
• This polymer softens and becomes plastic at a temperature of 70° to 90° C., but does not liquefy; for adhesion, it is necessary to laminate on a light coating of heat-sensitive adhesive.
• the material most commonly used as a heat-sensitive adhesive is a blend of a polyethylene vinyl acetate copolymer with resins and other additives. Also used as adhesives are cyclic ester polymers or copolymers and blends of these known polymers with polycaprolactone, in accordance with U.S. Pat. No.
• Another material widely used to reinforce toecaps is a polyamide copoylmer (for example, U.S. Pat. No. 4,122,229), which is applied in molten form; in this case, the adhesive itself is also the reinforcing material.
• a polyamide copoylmer for example, U.S. Pat. No. 4,122,229
• Another material used consists of a blend of ground plastic particles and polycaprolactone in accordance with the German patent cited.
• the ground plastic is used as a filler and polycaprolactone as the agglutinant.
• the agglutinant of the reinforcing material sometimes also serves as an adhesive.
• ionomer sheet extrusions are ionomer sheet extrusions; these polymers have the particular property of melting at low temperatures of 80°-90° C.; once cooled, they have excellent elastic rigidity and a high viscosity, which therefore prevents direct adhesion and makes the lamination of heat-sensitive layers of adhesive necessary.
• multilaminated materials made of combinations of the above-mentioned woven and non-woven materials, impregnated or not, and sheets of polymers extruded in fine layers are also used.
• thermoplastic polymers are used for the production of thermoplastic reinforcing materials.
• the thermoplastic polymers are used in the polymerized state. This means that, for processing them, they have to be transformed physically by supplying energy to melt them.
• the molten polymers have a viscosity that increases with the molecular weight and decreases as the temperature increases.
• the viscosity For the processing, it is desirable for the viscosity to be low, so that polymers can be worked with greater ease; in the case of compound materials, the low viscosity makes it possible to wet the fibers or particles of filler.
• the binding power and strength of polymers is proportional to their molecular weight, the polymers with the greatest binding power being the most appropriate for reinforcing materials. The solution is to raise the processing temperature which degrades the polymers and entails an expenditure of energy, since the polymers have to be cooled again after the processing.
• the polymers utilized have molecular weights and softening temperatures determined by their manufacturers and, while there are different grades, it is not possible to regulate them to meet the optimum requirements of each application.
• This invention relates to a method for the manufacture of reinforced thermoplastic and thermoadhesive polymers used to form reinforcing pieces for footwear, and includes:
• epsilon caprolactone and precursor blends of polyurethane which include polyisocyanates and polyols or polyolpolyesters in the presence of reinforcing materials and, optionally, of filling materials, under polymerization conditions and then shaping the polymer material formed by lamination, said reinforcing material comprising filaments, fibrous particles or microgranules.
• Another object of the invention is a method for the production of reinforced thermoplastic and thermoadhesive polymers that can be used to form reinforcing pieces for footwear, which includes:
• epsilon caprolactone and precursor blends of polyurethane which include polyisocyanates and polyols or polyolpolyesters in the presence of reinforcing materials and, optionally, of filling materials, under polymerization conditions and then shaping the polymer material formed by lamination, said reinforcing material comprising filaments, fibrous particles or microgranules while the lined reinforcing material includes woven filaments of between 5 and 30 dtex.
• Another inventive method is a process for the manufacture of reinforced thermoplastic and thermoadhesive polymers that can be used to form reinforcing components for footwear, which includes
• epsilon caprolactone and precursor blends of polyurethane which include polyisocyanates and polyols or polyolpolyesters in the presence of reinforcing materials, and, optionally, of filling materials, under polymerization conditions and then shaping the polymer material formed by lamination, said reinforcing material comprising filaments, fibrous particles or microgranules where the filling material is calcium carbonate or powdered sodium silicate or ground wood.
• the object of the invention is to obtain a compound reinforcing material, produced by the direct polymerization of monomers in contact with the filling and reinforcing materials.
• the advantage is that it is possible to work with various fibrous and powdered filling materials, since the monomers, because of their low viscosity, can efficiently wet all types of fillers and fibers.
• manufacturing costs are lowered because the number of processing steps is reduced by one, with the result that energy consumption is reduced.
• certain parameters can be controlled, such as the final molecular weight and the polymer softening temperature, to meet the precise needs of the user.
• polyols for the purposes of this invention, it is possible to use as monomers polyols, diols, caprolactone monomer, diisocyanates which, upon reacting chemically, form polyurethanes, or a caprolactone monomer which, upon reacting, is polymerized into polycaprolactone.
• Suitable diisocyanates include, but are not limited to, methylene diisocyanate, hexamethylene diisocyanate, 2,4-toluene diisocyanate, and diphenylmethane diisocyanate.
• Suitable polyols include, but are not limited to, condensation products of sebacic acid, azelaic acid, or adipic acid esterified with hexylene glycol, butylene glycol, or ethylene glycol.
• polymerization is carried out using conventional techniques, but in the presence of the structural filling materials, namely fillers, fibers or fabric.
• the final product is obtained directly in its final physical form and is then cooled after polymerization in a continuous cooler, forming a sheet of the desired thickness.
• fillers does not affect the quality of polymerization, because they are inert.
• the moisture is eliminated by heating and vacuum.
• the presence of fillers does not entail a greater expenditure of thermal energy for the polymerization; the small increase in mechanical energy, necessary for homogenization, is negligible since fillers are introduced at the outset, when the viscosity is low; in the final phase, the viscosity is the highest and the presence of fillers has little impact.
• This invention proposes another possible alternative, which has been tested experimentally to produce reinforced, thermoplastic and thermoadhesive materials and consists of the introduction of fillers--in powdered, granulated or filament form--during the process of forming the thermoplastic polymer, so that once polymerization is completed, reinforced polymers are obtained, shaped into sheets, plates, etc., or molded into units of pre-established form and size. Specifically involved are epsilon caprolactone polymers and polyurethanes.
• This operational alternative which constitutes the object of this invention, is advantageous in that the filling and reinforcing materials are moistened and penetrated by the monomers, the prepolymers formed with the remaining components of the medium, so that polymerization also takes place within the particles or filaments of the filling and/or reinforcing materials and the linkage or bonding between the polymerized matrix and the filling and/or reinforcing materials is increased.
• this alternative is advantageous from another standpoint, in that reinforced thermoplastic and thermoadhesive materials are obtained in a single operation, in contrast to conventional techniques, in which the introduction of those components occurs in a subsequent operation after the polymerization is completed.
• filler refers to materials incorporated into decorative and/or bulking polymers
• reinforcing materials are those, which are introduced for the purpose of improving certain properties, such as hardness, tensile strength, flexibility, etc., although such incorporation obviously can produce desirable aesthetic effects.
• the products of the inventive method are molded into sheets 0.1 to 3 mm thick or into units dimensioned for each type of shoe.
• polyol product of the esterification of 100 parts of sebacic acid with 1,6-dihydroxyhexane, hydroxyl number 57.2, acidity index 2.54
• filler 10 parts of short cotton fibers, 40 parts of ground wood, 50 parts of micronized calcium carbonate.
• a catalyst triethylenediamine, 0.2 parts
• the temperature is raised to 105° C. for 5 minutes and is then lowered to 85° C. at the outlet.
• Discharge is through a flat die into a cooler, formed by two stainless steel belts coated with a non-stick "fluoropolymer" material.
• the steel belts roll the material. Lamination thickness can be regulated in the admission cylinders.
• the steel belts are externally cooled by cold water, the material is crystallized between the belts and demolded in continuous form and then coiled.
• a polyol (100 parts, product of the esterification of sebacic acid and 1,6-dihydroxyhexane, hydroxyl number 57.2, acidity index 2.54) is loaded into a closed container with a mixer and heater. After the temperature is raised to 80° C., a 40 torr vacuum is maintained for 60 minutes. MDI diphenylmethane diisocyanate (32.5 parts) is added and allowed to react at 80° C. for 90 min. This prepolymer is known as component "A".
• the same polyol (100 parts, product of the esterification of sebacic acid and 1,6-dihydroxyhexane, hydroxyl number 57.2, acidity index 2.54) is loaded into another closed container with mixer and heater.
• 50 parts of micronized calcium carbonate are introduced as filler.
• a 40 torr vacuum is maintained for 60 minutes, whereupon 0.3 parts of a catalyst (triethylenetriamine) are added.
• This mixture is called component "B".
• components "A” and “B” are fed in the proportions of 40 parts of "A” to 100 parts of "B” into a high speed mixing die, which discharges the mixture onto a needle-punched non-woven polyester fiber of 200 g/m 2 .
• the material then immediately enters a unit consisting of two stainless steel belts coated with a non-stick "fluoropolymer” material.
• the steel bands roll the material.
• the thickness of lamination can be regulated on the admission cylinders.
• the first section of the steel belts is heated externally by infrared rays to a temperature of 100° C. to accelerate the polymerization reaction.
• the belts are externally cooled by cold water and the material crystallized between the belts and demolded in continuous form at the outlet and coiled.
• the following components are mixed in a closed container equipped with kneading arms having the capacity to handle highly viscous products and with a heating/cooling system: 100 parts of polyol (product of the esterification of sebacic acid and 1,6-dihydroxyhexane, hydroxyl number 57.2, acidity index 2.54), 100 parts of filler (10 parts of short polyamide fibers of 6.6 nylon, 2-3 mm long. Titer 15 dtex, 90 parts of ground PET polyester with a particle size of 500 microns). After the temperature is raised to 80° C., a 40 torr vacuum is maintained for 60 minutes. After 12.5 parts diphenylmethane diisocyanate are added, the mixture is maintained at 95° C. for 60 minutes and then at 85° C.
• polyol product of the esterification of sebacic acid and 1,6-dihydroxyhexane, hydroxyl number 57.2, acidity index 2.54
• filler 10 parts of short polyamide fibers of 6.6 nylon, 2-3 mm long.
• the steel belts roll the material.
• the lamination thickness can be regulated in the admission cylinders.
• the steel belts are externally cooled by cold water, the material is crystallized between the belts and demolded in continuous form at the outlet and then coiled.
• the following components are mixed in a closed container equipped with kneading arms having the ability to handle highly viscous products and with a heating/cooling system: 110 parts of an epsilon caprolactone monomer, 100 parts of filler (10 parts micronized calcium carbonate, 90 parts ground wood particle size 500 micros). After the temperature is raised to 80° C., a 40 torr vacuum is maintained for 60 minutes, 2 parts 1-6-dihydroxyhexane and 0.4 parts tetraisopropyl titanate as a catalyst are added. The temperature is then raised to 165° C. for 180 minutes and lowered to 85° C.
• the product is discharged by means of a screw pump and a flat die into a cooler, formed by two stainless steel belts coated with a non-stick "fluoropolymer" material.
• the steel belts roll the material; the rolling thickness in the cylinder can be regulated externally by cold water.
• the material is crystallized between the belts and demolded in continuous form at the outlet from the cooler, then coiled.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
• Polyurethanes Or Polyureas (AREA)

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Cited By (7)

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Citations (6)

• 1996
  • 1996-09-13 US US08/713,725 patent/US6100328A/en not_active Expired - Fee Related
• 1997
  • 1997-09-12 AR ARP970104193A patent/AR009774A1/es active IP Right Grant
  • 1997-09-15 BR BR9702876-2A patent/BR9702876A/pt not_active IP Right Cessation
  • 1997-09-15 CN CN97116535A patent/CN1105146C/zh not_active Expired - Fee Related

Patent Citations (6)

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